CN115287737B - Titanium-based gradient composite manganese dioxide anode plate and preparation method thereof - Google Patents
Titanium-based gradient composite manganese dioxide anode plate and preparation method thereof Download PDFInfo
- Publication number
- CN115287737B CN115287737B CN202210928867.8A CN202210928867A CN115287737B CN 115287737 B CN115287737 B CN 115287737B CN 202210928867 A CN202210928867 A CN 202210928867A CN 115287737 B CN115287737 B CN 115287737B
- Authority
- CN
- China
- Prior art keywords
- titanium
- composite
- anode plate
- coated
- sbox
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 444
- 239000010936 titanium Substances 0.000 title claims abstract description 339
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 339
- 239000002131 composite material Substances 0.000 title claims abstract description 211
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 109
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 109
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 51
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 50
- 238000004070 electrodeposition Methods 0.000 claims abstract description 34
- 229910018316 SbOx Inorganic materials 0.000 claims description 112
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 111
- 239000011521 glass Substances 0.000 claims description 84
- 229910052799 carbon Inorganic materials 0.000 claims description 67
- 229910003070 TaOx Inorganic materials 0.000 claims description 64
- 239000011246 composite particle Substances 0.000 claims description 60
- 239000007788 liquid Substances 0.000 claims description 59
- 239000011248 coating agent Substances 0.000 claims description 58
- 238000000576 coating method Methods 0.000 claims description 58
- 238000005245 sintering Methods 0.000 claims description 58
- 239000011324 bead Substances 0.000 claims description 56
- 239000002243 precursor Substances 0.000 claims description 56
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 51
- 238000007747 plating Methods 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 28
- 239000004005 microsphere Substances 0.000 claims description 28
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 claims description 26
- 229910052787 antimony Inorganic materials 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 238000003466 welding Methods 0.000 claims description 25
- 229910052718 tin Inorganic materials 0.000 claims description 24
- 150000003608 titanium Chemical class 0.000 claims description 24
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 21
- 230000002378 acidificating effect Effects 0.000 claims description 21
- 239000004917 carbon fiber Substances 0.000 claims description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 18
- 235000006408 oxalic acid Nutrition 0.000 claims description 17
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 13
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 12
- 238000005488 sandblasting Methods 0.000 claims description 12
- 238000004381 surface treatment Methods 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000012212 insulator Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- -1 tin ruthenium tantalum Chemical compound 0.000 claims description 10
- LTNGUMKBFWBWGY-UHFFFAOYSA-N [Sb][Sn][Pt] Chemical compound [Sb][Sn][Pt] LTNGUMKBFWBWGY-UHFFFAOYSA-N 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 8
- 238000005098 hot rolling Methods 0.000 claims description 8
- FAUWSVSZYKETJJ-UHFFFAOYSA-N palladium titanium Chemical compound [Ti].[Pd] FAUWSVSZYKETJJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 6
- VRAIHTAYLFXSJJ-UHFFFAOYSA-N alumane Chemical compound [AlH3].[AlH3] VRAIHTAYLFXSJJ-UHFFFAOYSA-N 0.000 claims description 6
- WPPDFTBPZNZZRP-UHFFFAOYSA-N aluminum copper Chemical compound [Al].[Cu] WPPDFTBPZNZZRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005238 degreasing Methods 0.000 claims description 6
- 238000009713 electroplating Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 6
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910020935 Sn-Sb Inorganic materials 0.000 claims description 4
- 229910008757 Sn—Sb Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 229910000978 Pb alloy Inorganic materials 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 128
- 239000011701 zinc Substances 0.000 description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 15
- 229910052725 zinc Inorganic materials 0.000 description 15
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 12
- 239000011229 interlayer Substances 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 229910052721 tungsten Inorganic materials 0.000 description 7
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005363 electrowinning Methods 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000010405 anode material Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910001924 platinum group oxide Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention relates to a titanium-based gradient composite manganese dioxide anode plate and a preparation method thereof, belonging to the technical field of nonferrous metal electrodeposition. The titanium-based gradient composite manganese dioxide anode plate comprises a titanium-coated aluminum conductive beam and a titanium-based oxide anode plate, wherein the titanium-based oxide anode plate comprises a titanium plate, titanium-coated aluminum composite rods, double-layer titanium meshes and titanium rods, the top end of the titanium plate is fixedly connected with the bottom end of the titanium-coated aluminum conductive beam, the titanium-coated aluminum composite rods are vertically arranged at the bottom end of the titanium plate, the double-layer titanium meshes are arranged between adjacent titanium-coated aluminum composite rods, the titanium rods are arranged at the bottom ends of the titanium-coated aluminum composite rods, the top ends of the double-layer titanium meshes are fixedly connected with the titanium plate, and the bottom ends of the double-layer titanium meshes are fixedly connected with the titanium rods; the titanium surfaces of the titanium plate, the titanium-coated aluminum composite rod, the double-layer titanium mesh and the titanium rod are sequentially coated with a metal oxide intermediate layer and a composite manganese dioxide active layer. Compared with the traditional lead alloy anode, the invention has the advantages of reduced cell voltage, prolonged service life, improved current efficiency and high quality of cathode products.
Description
Technical Field
The invention relates to a titanium-based gradient composite manganese dioxide anode plate and a preparation method thereof, belonging to the technical field of nonferrous metal electrodeposition.
Background
During non-ferrous metallurgy, more than about 90% of the zinc and about 30% of the copper are extracted by hydrometallurgical techniques. In particular, in the zinc hydrometallurgy process, the electrowinning process consumes 2/3 of the energy consumption of the whole zinc extraction process, and the production energy consumption of zinc hydrometallurgy ton is 3200-4200 kwh/t.Zn. The oxygen evolution potential of the industrial lead alloy anode is up to about 1V, so that the useless electricity consumption is increased by about 1000kWh, and the useless electricity consumption accounts for about 30% of the total energy consumption of zinc electrowinning.
The anode materials used at home and abroad at present mainly comprise the following four types:
first category lead alloy anode: the defects of poor corrosion resistance, toxicity, harm to human bodies, solution pollution, easy deformation in the electrolysis process, precipitation at a cathode and the like are caused, and the anode pollution of the produced lead-base alloy is large, so that the lead-base alloy does not accord with the national policy and is gradually eliminated by the market;
A second class of titanium-based platinum-group oxide-coated anodes: the noble metal coating titanium anode has better performance, no consumption in the electrolysis process, good stability, low oxygen evolution overpotential and high catalytic activity, but the high price limits the large-scale application of the noble metal coating titanium anode;
Third class titanium-based lead dioxide coated anode: the titanium-based lead dioxide anode inherits the advantages of the coating titanium anode and the lead anode, fully combines the advantages of good shape stability of the titanium anode and price of the lead anode, and fully overcomes the defects of easy corrosion, easy bending, high price of the coating titanium anode and the like of the lead anode. But the following problems occur in use: (1) The PbO 2 deposition layer is not tightly combined with the surface of the electrode or the deposition layer is not uniform; (2) The PbO 2 deposition layer has ceramic brittleness, and the denser internal stress is larger; (3) The conductive corrosion-resistant beta-PbO 2 deposition layer has weak bonding force with the titanium matrix, and is easy to fall off in the use process; (4) The PbO 2 electrode has a high cell voltage in electrodeposition applications.
Fourth class titanium-based manganese dioxide coated anode: the manganese dioxide coated anode has the advantages that: the oxygen evolution overpotential is low, the corrosion resistance is good, and the purity of the cathode product is high; the defects are as follows: the preparation process is complex and the cost is high; in addition, the manganese dioxide coating anode mostly has obvious cracks on the surface, the substrate is easy to expose in the long-time electrolysis process, the corrosion rate of the metal substrate is increased, if the substrate is titanium-based, nonconductive titanium dioxide is generated on the exposed substrate surface by oxidation, and the voltage and the energy consumption are increased.
In addition, the titanium-based anode produced in the current industrial production is easy to deform in actual use, so that the cathode and anode are easy to be short-circuited, the anode is seriously damaged, the power consumption is increased, and the quality of the cathode product is reduced.
Therefore, development of an anode having high current efficiency, low energy consumption, low cost, simple process, and high quality of cathode products (low lead content) is urgently needed.
Disclosure of Invention
Aiming at the problems that in industrial production, a titanium-based anode is easy to deform in actual use, the cathode and anode are extremely easy to be short-circuited, the anode is seriously damaged, the power consumption is increased, and the quality of a cathode product is reduced, the invention provides the titanium-based gradient composite manganese dioxide anode plate and the preparation method thereof, and the Ag-doped carbon fiber-beta-PbO 2 composite particles are embedded into a tungsten-containing gamma-MnO 2 coating, so that the conductivity of gamma-MnO 2 is greatly improved, the internal stress of the coating is reduced, the service life of a composite manganese dioxide electrode is prolonged, and the cell voltage is reduced; meanwhile, the Sn-Ru-TaOx coated hollow glass beads are embedded into the tungsten-containing gamma-MnO 2 coating, so that the catalytic activity of gamma-MnO 2 is improved, the brittleness of the gamma-MnO 2 coating is greatly reduced, and the stability of the electrode in the use process is better; compared with the traditional lead alloy anode, the cell voltage of the titanium-based gradient composite manganese dioxide anode plate is reduced by more than 8%, the service life is prolonged by more than 1 time, the current efficiency is improved by more than 2%, and the quality of a cathode product is high.
The titanium-based gradient composite manganese dioxide anode plate comprises a titanium-coated aluminum conductive beam 1 and a titanium-based oxide anode plate 2, wherein the titanium-based oxide anode plate 2 is fixedly arranged at the bottom end of the titanium-coated aluminum conductive beam 1, and an insulator 7 is arranged on the titanium-based oxide anode plate 2;
The titanium-based oxide anode plate 2 comprises a titanium plate 3, titanium-coated aluminum composite rods 4, double-layer titanium nets 5 and titanium rods 6, wherein the top end of the titanium plate 3 is fixedly connected with the bottom end of a titanium-coated aluminum conductive beam 1, the titanium-coated aluminum composite rods 4 are vertically arranged at the bottom end of the titanium plate 3, the titanium rods 6 are arranged at the bottom end of the titanium-coated aluminum composite rods 4, the titanium plate 3, the titanium-coated aluminum composite rods 4 and the titanium rods 6 form a titanium-based oxide anode plate frame, the double-layer titanium nets 5 are arranged between adjacent titanium-coated aluminum composite rods 4, the top ends of the double-layer titanium nets 5 are fixedly connected with the titanium plate 3, and the bottom ends of the double-layer titanium nets 5 are fixedly connected with the titanium rods 6; the titanium surface of the titanium-based oxide anode plate frame is sequentially coated with a metal oxide intermediate layer I and a composite manganese dioxide active layer, and the titanium surface of the double-layer titanium mesh 5 is sequentially coated with a metal oxide intermediate layer II and a composite manganese dioxide active layer.
The thickness of the titanium layer of the titanium-coated aluminum conductive beam 1 is 1-3 mm, one end of the titanium-coated aluminum conductive beam 1 is welded with a copper-aluminum composite conductive head, the thickness of a titanium plate 3 is 3-5 mm, the thickness of the titanium layer of the titanium-coated aluminum composite rod 4 is 0.5-2 mm, the long axis of the double-layer titanium mesh 5 is 3-16 mm, the short axis is 1-6 mm, and the section thickness is 0.5-3 mm; the thickness of the metal oxide intermediate layer I and the metal oxide intermediate layer II is 1-5 mu m, and the thickness of the composite manganese dioxide active layer is 0.3-2 mm.
The metal oxide intermediate layer I is Sn-SbOx, the metal oxide intermediate layer II is a Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer or a Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer, and the composite manganese dioxide active layer contains Ag-carbon fiber-beta-PbO 2 doped composite particles, sn-Ru-TaOx coated hollow glass beads and gamma-MnO 2.
Further, the granularity of the carbon fiber is 1-10 mu m, the granularity of the Ag-carbon fiber-beta-PbO 2 -doped composite particle is 10-100 mu m, and the granularity of the hollow glass bead is 10-100 mu m.
Further, the molar ratio of Pt, sn and Sb in the Pt-Sn-SbOx is 1-7:80-87:6-19, the molar ratio of Pd, ti, sn and Sb in the Pd-Ti-Sn-SbOx is 1-5:3-8:70-85:2-24, and the molar ratio of Sn and Sb in the Sn-SbOx is 70-80:20-30.
Further, based on the mass percentage of 100% of the composite manganese dioxide active layer, 1-6% of Ag-carbon fiber-beta-PbO 2 composite particles, 0.5-4% of Sn-Ru-TaOx coated hollow glass microspheres, 0.05-2% of W and the balance of gamma-MnO 2 are mixed; the Ag-carbon fiber-beta-PbO 2 composite particles contain 0.5-5% of Ag, 0.1-1% of carbon fiber powder and the balance of beta-PbO 2; the molar ratio of Sn, ru and Ta in the Sn-Ru-TaOx coated hollow glass microsphere is 40-50:30-42:8-30, and the Sn-Ru-TaOx oxide accounts for 1-8% of the mass of the Sn-Ru-TaOx coated hollow glass microsphere.
Further, the preparation method of the Ag-doped carbon fiber-beta-PbO 2 composite particles comprises the following specific steps:
Electrodepositing stainless steel serving as an anode and a titanium mesh serving as a cathode in an acidic lead nitrate composite plating solution for 4-8 hours to obtain an Ag-doped carbon fiber-beta-PbO 2 composite plating layer, stripping the Ag-doped carbon fiber-beta-PbO 2 composite plating layer, and performing ball milling to obtain Ag-doped carbon fiber-beta-PbO 2 composite particles; wherein the acidic lead nitrate composite plating solution contains 50-200 g/L of lead nitrate, 0.5-20 g/L of silver nitrate, 4-20 g/L of thiourea and 4-20 g/L of carbon fiber particles, and the pH value of the acidic lead nitrate composite plating solution is 0-2; the temperature of the electrodeposition is 60-90 ℃ and the current density is 6-12A/dm 2.
Further, the preparation method of the Sn-Ru-TaOx coated hollow glass microsphere comprises the following specific steps:
1) Dissolving tin chloride, ruthenium chloride and tantalum chloride in concentrated hydrochloric acid, adding n-butanol solvent, and removing water by rotary evaporation to obtain tin ruthenium tantalum precursor liquid;
2) Calcining the hollow glass beads for 0.5-2 h at 400-600 ℃, immersing in a NaOH solution with the concentration of 5-10 wt.%, treating for 5-40 min at 60-90 ℃, immersing in an HF solution with the concentration of 0.5-2 wt.% for 1-5 min after washing with deionized water, deionized washing, and drying to obtain pretreated hollow glass beads;
3) Immersing the pretreated hollow glass beads in tin-ruthenium-tantalum precursor liquid for ultrasonic immersing for 5-10 min, drying at 100-150 ℃, roasting at 300-560 ℃ for 10-20 min, repeating the ultrasonic immersing and roasting processes for 6-12 times, and sintering at 400-480 ℃ for 1-2 h to obtain the Sn-Ru-TaOx coated hollow glass bead composite particles.
The preparation method of the titanium-based gradient composite manganese dioxide anode plate comprises the following specific steps:
(1) Soaking the aluminum bar in NaOH solution for 1-5 min after degreasing and pickling, cleaning by deionized water, and then soaking in HNO 3 solution for 4-8 min for activation to obtain an activated aluminum bar; the inner wall of the titanium tube is treated by HF solution, and is cleaned by deionized water to obtain a pretreated titanium tube; the pretreated titanium tube is sleeved outside the aluminum rod and is extruded, drawn and compounded, the titanium-coated aluminum composite rod is obtained through hot rolling, and the titanium-coated aluminum composite rod and the aluminum-copper composite conductive head are welded to obtain a titanium-coated aluminum conductive beam;
(2) Welding a titanium plate, a titanium coated aluminum composite rod and a titanium rod to form a titanium-based oxide anode plate frame, immersing the titanium-based oxide anode plate frame in NaOH solution for 10-30 min, performing heat treatment on the titanium-based oxide anode plate frame after sand blasting surface treatment, then placing the titanium-based oxide anode plate frame in oxalic acid solution for activating for 0.5-2.0 h to obtain an activated titanium-based oxide anode plate frame, coating tin-antimony precursor liquid on the surface of the activated titanium-based oxide anode plate frame, drying, performing sintering pretreatment for 5-10 min, repeating the steps of coating tin-antimony precursor liquid and sintering for 3-10 times, and then placing the titanium-based oxide anode plate frame coated with a metal oxide intermediate layer at the temperature of 400-600 ℃ for sintering for 1-2 h to obtain the titanium-based oxide anode plate frame coated with the metal oxide intermediate layer;
(3) Immersing a drawn titanium mesh in NaOH solution for 10-30 min, performing heat treatment after sand blasting surface treatment on the titanium mesh, then placing the titanium mesh in oxalic acid solution for activation for 0.5-2.0 h to obtain an activated titanium mesh, coating platinum tin antimony precursor liquid or palladium titanium tin antimony precursor liquid on the surface of the activated titanium mesh, drying, performing sintering pretreatment for 5-10 min, repeating the coating and sintering processes for 3-10 times, and then placing the titanium mesh at 400-600 ℃ for sintering for 1-2 h to obtain the titanium mesh coated with Pt-Sn-SbOx or Pd-Ti-Sn-Sb; coating tin-antimony precursor liquid on the surface of the titanium mesh coated with Pt-Sn-SbOx or Pd-Ti-Sn-Sb, drying, then sintering and pre-treating for 5-10 min, repeating the steps of coating tin-antimony precursor liquid and sintering for 3-10 times, and then sintering for 1-2 h at the temperature of 400-600 ℃ to obtain the titanium mesh coated with the Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer or Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer;
(4) Welding a titanium mesh coated with a Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer or a Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer on a titanium-based oxide anode plate frame coated with a metal oxide intermediate layer to form a titanium-based oxide anode plate blank, wherein the titanium mesh coated with the Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer or the Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer is positioned between adjacent titanium-clad aluminum composite rods; placing a titanium-based oxide anode plate blank serving as an anode and a titanium plate serving as a cathode in a manganese nitrate composite electroplating solution for composite electrodeposition, cleaning with deionized water, and drying to obtain a titanium-based oxide anode plate;
(5) And welding the top end of a titanium plate of the titanium-based oxide anode plate to the bottom end of a titanium-coated aluminum conductive beam, and mounting an insulator on the titanium-based oxide anode plate to obtain the titanium-based gradient composite manganese dioxide anode plate.
The concentration of NaOH solution in the step (1) is 5-10 wt%, the soaking temperature of NaOH solution is 40-70 ℃, the concentration of HNO 3 solution is 10-40 wt%, the concentration of HF solution is 1-10 wt%, the hot rolling temperature is 500-700 ℃, and the welding method is pulse argon protection aluminum-aluminum welding;
the concentration of the NaOH solution in the step (2) is 10-20 wt%, the soaking temperature of the NaOH solution is 50-80 ℃, the heat treatment temperature is 400-700 ℃, the heat treatment time is 0.2-1.5 h, the concentration of the oxalic acid solution is 5-30 wt%, the activation temperature is 80-100 ℃, and the sintering pretreatment temperature is 400-700 ℃;
The concentration of NaOH solution in the step (3) is 10-20 wt%, the soaking temperature of NaOH solution is 50-80 ℃, the heat treatment temperature is 400-700 ℃, the heat treatment time is 0.2-1.5 h, the concentration of oxalic acid solution is 5-30 wt%, the activation temperature is 80-100 ℃, and the sintering pretreatment temperature is 400-700 ℃;
The temperature of the composite electrodeposition in the step (4) is 80-100 ℃, the current density is 1-5A/dm 2, the stirring speed is 50-300 rpm, and the composite electrodeposition time is 4-20 h; the manganese nitrate composite plating solution contains 20-100 g/L manganese nitrate (Mn (NO 3)2), 2-30 g/L nitric acid (HNO 3), 10-40 g/L sodium tungstate (Na 2WO4), 10-30 g/L Ag-doped carbon fiber-beta-PbO 2 composite particles and 4-30 g/L Sn-Ru-TaOx coated hollow glass microspheres.
The preparation method of the palladium titanium tin antimony precursor liquid comprises the following steps: adding palladium chloride, tetrabutyl titanate, tin chloride and antimony chloride into concentrated hydrochloric acid according to a molar ratio until the palladium chloride, the tetrabutyl titanate, the tin chloride and the antimony chloride are completely dissolved, then adding an n-butanol solvent, and removing water of the coating liquid by adopting a rotary evaporator to obtain palladium titanium tin antimony precursor liquid;
The preparation of the platinum tin antimony precursor liquid comprises the following steps: adding chloroplatinic acid (H 2PtC16·6H2 O), stannic chloride and antimony chloride into concentrated hydrochloric acid according to a molar ratio until the chloroplatinic acid, the stannic chloride and the antimony chloride are completely dissolved, then adding n-butanol solvent, and removing water of the coating liquid by adopting a rotary evaporator to obtain platinum-tin-antimony precursor liquid;
The preparation of the tin-antimony precursor liquid comprises the following steps: adding tin chloride and antimony chloride into concentrated hydrochloric acid according to a molar ratio until the tin chloride and the antimony chloride are completely dissolved, then adding n-butanol solvent, and removing water of the coating liquid by adopting a rotary evaporator to obtain tin-antimony precursor liquid.
The beneficial effects of the invention are as follows:
(1) The titanium-based gradient composite manganese dioxide anode plate is used for nonferrous metal electrodeposition, and has the advantages of good electrocatalytic activity, long service life, low cost and high electric efficiency; compared with the traditional lead-based multielement alloy, the cell voltage can be reduced by more than 8 percent on the basis of not changing the structure, the electrolyte composition and the operation specification of the electrolytic cell, the service life is prolonged by more than 1 time, the current efficiency is improved by more than 2 percent, and the quality of cathode products is high;
(2) The invention adopts the titanium-coated aluminum conductive beam/bar, which not only can reduce the material cost of the electrode, but also can avoid the introduction of impurity ions (Cu 2+) into the cathode product;
(3) According to the titanium-based gradient composite manganese dioxide anode plate, pd and Pt elements are introduced into the metal oxide interlayer, so that the surface area of the coating can be increased, the coating is easy to become a net structure, the conductivity of the coating is increased, and the interface resistance between the titanium-based and the coating is reduced;
(4) The invention adopts the double-layer titanium mesh electrode, so that the apparent area of the electrode surface is increased by 1 time, the catalytic activity of the active layer is improved, and the cell voltage of the electrode in the electro-deposition process is reduced;
(5) According to the invention, ag-carbon fiber-beta-PbO 2 doped composite particles are embedded into the tungsten-containing gamma-MnO 2 coating, so that the electric conductivity of gamma-MnO 2 is greatly improved, the internal stress of the coating is reduced, the service life of the composite manganese dioxide electrode is prolonged, and the cell voltage is reduced; meanwhile, the Sn-Ru-TaOx coated hollow glass beads are embedded into the tungsten-containing gamma-MnO 2 coating, so that the catalytic activity of gamma-MnO 2 is improved, the brittleness of the gamma-MnO 2 coating is greatly reduced, and the stability of the electrode in the use process is better; the addition of Ag-carbon fiber-beta-PbO 2 composite particles and Sn-Ru-TaOx coated hollow glass beads in the electrodeposited manganese dioxide plating solution can increase the current density of the electrodeposited anode by more than 4 times, and does not generate a rough gamma-MnO 2 plating layer.
Drawings
FIG. 1 is a schematic diagram of a titanium-based gradient composite manganese dioxide anode plate;
FIG. 2 is a schematic view in section A-A of FIG. 1;
FIG. 3 is a schematic view of section B-B of FIG. 2;
FIG. 4 is a schematic view of section C-C of FIG. 1;
In the figure: 1-titanium coated aluminum conductive beam, 1 a-copper aluminum composite conductive head, 2-titanium-based oxide anode plate, 3-titanium plate, 4-titanium coated aluminum composite rod, 5-double-sided titanium net, 5 a-titanium matrix, 5 b-metal oxide intermediate layer, 5 c-composite manganese dioxide active layer, 6-titanium rod and 7-insulator.
Detailed Description
The invention will be described in further detail with reference to specific embodiments, but the scope of the invention is not limited to the description.
The invention relates to a titanium-based gradient composite manganese dioxide anode plate (see figures 1-4), which comprises a titanium-coated aluminum conductive beam 1 and a titanium-based oxide anode plate 2, wherein the titanium-based oxide anode plate 2 is fixedly arranged at the bottom end of the titanium-coated aluminum conductive beam 1, and an insulator 7 is arranged on the titanium-based oxide anode plate 2;
The titanium-based oxide anode plate 2 comprises a titanium plate 3, titanium-coated aluminum composite rods 4, double-layer titanium nets 5 and titanium rods 6, wherein the top end of the titanium plate 3 is fixedly connected with the bottom end of a titanium-coated aluminum conductive beam 1, the titanium-coated aluminum composite rods 4 are vertically arranged at the bottom end of the titanium plate 3, the titanium rods 6 are arranged at the bottom end of the titanium-coated aluminum composite rods 4, the titanium plate 3, the titanium-coated aluminum composite rods 4 and the titanium rods 6 form a titanium-based oxide anode plate frame, the double-layer titanium nets 5 are arranged between adjacent titanium-coated aluminum composite rods 4, the top ends of the double-layer titanium nets 5 are fixedly connected with the titanium plate 3, and the bottom ends of the double-layer titanium nets 5 are fixedly connected with the titanium rods 6; the titanium surface of the titanium-based oxide anode plate frame is sequentially coated with a metal oxide intermediate layer I and a composite manganese dioxide active layer, and the titanium surface of the double-layer titanium mesh 5, namely the titanium substrate 5a is sequentially coated with a metal oxide intermediate layer II5b and a composite manganese dioxide active layer 5c;
The length of the titanium-coated aluminum conductive beam 1 is 600-1500 mm, the width is 20-50 mm, the height is 30-60 mm, the thickness of the titanium layer of the titanium-coated aluminum conductive beam 1 is 1-3 mm, one end of the titanium-coated aluminum conductive beam 1 is welded with a copper-aluminum composite conductive head 1a, the length of the copper-aluminum composite conductive head 1a is 50-200 mm, the width is 20-50 mm, the height is 10-30 mm, the thickness of the titanium plate 3 is 3-5 mm, the titanium-coated aluminum composite rod 4 is round or square, and the diameter of round rod aluminum is The section length of square aluminum is 4-10 mm, the width is 1-4 mm, the thickness of the titanium layer of the titanium-coated aluminum composite rod 4 is 0.5-2 mm, the long axis of the double-layer titanium mesh 5 is 3-16 mm, and the short axis is 1-6 mm; the titanium rod 6 is a round rod or a square rod, wherein the diameter of the round rod isThe section of the square bar is 4-10 mm long and 3-5 mm wide; the thickness of the metal oxide intermediate layer I and the metal oxide intermediate layer II is 1-5 mu m, and the thickness of the composite manganese dioxide active layer is 0.3-2 mm;
The metal oxide intermediate layer I is Sn-SbOx, the metal oxide intermediate layer II is a Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer or a Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer, and the composite manganese dioxide active layer contains Ag-carbon fiber-beta-PbO 2 doped composite particles, sn-Ru-TaOx coated hollow glass beads and gamma-MnO 2;
The granularity of the carbon fiber is 1-10 mu m, the granularity of the Ag-carbon fiber-beta-PbO 2 doped composite particle is 10-100 mu m, and the granularity of the hollow glass bead is 10-100 mu m;
the mol ratio of Pt, sn and Sb in Pt-Sn-SbOx is 1-7:80-87:6-19, the mol ratio of Pd, ti, sn and Sb in Pd-Ti-Sn-SbOx is 1-5:3-8:70-85:2-24, and the mol ratio of Sn and Sb in Sn-SbOx is 70-80:20-30;
The mass percentage of the composite manganese dioxide active layer is 100 percent, the composite particles doped with Ag-carbon fiber-beta-PbO 2 account for 1 to 6 percent, the hollow glass beads coated with Sn-Ru-TaOx account for 0.5 to 4 percent, the W accounts for 0.05 to 2 percent, and the balance is gamma-MnO 2; the Ag-carbon fiber-beta-PbO 2 composite particles contain 0.5-5% of Ag, 0.1-1% of carbon fiber powder and the balance of beta-PbO 2; the molar ratio of Sn, ru and Ta in the Sn-Ru-TaOx coated hollow glass microsphere is 40-50:30-42:8-30, and the Sn-Ru-TaOx oxide accounts for 1-8% of the mass of the Sn-Ru-TaOx coated hollow glass microsphere;
the preparation method of the Ag-carbon fiber-beta-PbO 2 -doped composite particle comprises the following specific steps:
Electrodepositing stainless steel serving as an anode and a titanium mesh serving as a cathode in an acidic lead nitrate composite plating solution for 4-8 hours to obtain an Ag-doped carbon fiber-beta-PbO 2 composite plating layer, stripping the Ag-doped carbon fiber-beta-PbO 2 composite plating layer, and performing ball milling to obtain Ag-doped carbon fiber-beta-PbO 2 composite particles; wherein the acidic lead nitrate composite plating solution contains 50-200 g/L of lead nitrate, 0.5-20 g/L of silver nitrate, 4-20 g/L of thiourea and 4-20 g/L of carbon fiber particles, and the pH value of the acidic lead nitrate composite plating solution is 0-2; the temperature of the electrodeposition is 60-90 ℃ and the current density is 6-12A/dm 2;
the preparation method of the Sn-Ru-TaOx coated hollow glass microsphere comprises the following specific steps:
1) Dissolving tin chloride, ruthenium chloride and tantalum chloride in concentrated hydrochloric acid, adding n-butanol solvent, and removing water by rotary evaporation to obtain tin ruthenium tantalum precursor liquid;
2) Calcining the hollow glass beads for 0.5-2 h at 400-600 ℃, immersing in a NaOH solution with the concentration of 5-10 wt.%, treating for 5-40 min at 60-90 ℃, immersing in an HF solution with the concentration of 0.5-2 wt.% for 1-5 min after washing with deionized water, deionized washing, and drying to obtain pretreated hollow glass beads;
3) Immersing the pretreated hollow glass beads in tin-ruthenium-tantalum precursor liquid for ultrasonic immersing for 5-10 min, drying at 100-150 ℃, roasting at 300-560 ℃ for 10-20 min, repeating the ultrasonic immersing and roasting processes for 6-12 times, and sintering at 400-480 ℃ for 1-2 h to obtain Sn-Ru-TaOx coated hollow glass bead composite particles;
According to the invention, ag-carbon fiber-beta-PbO 2 doped composite particles are embedded into the tungsten-containing gamma-MnO 2 coating, so that the electric conductivity of gamma-MnO 2 is greatly improved, the internal stress of the coating is reduced, the service life of the composite manganese dioxide electrode is prolonged, and the cell voltage is reduced; meanwhile, the Sn-Ru-TaOx coated hollow glass beads are embedded into the tungsten-containing gamma-MnO 2 coating, so that the catalytic activity of gamma-MnO 2 is improved, the brittleness of the gamma-MnO 2 coating is greatly reduced, and the stability of the electrode in the use process is better; the addition of Ag-carbon fiber-beta-PbO 2 composite particles and Sn-Ru-TaOx coated hollow glass beads in the electrodeposited manganese dioxide plating solution can increase the current density of the electrodeposited anode by more than 4 times, and does not generate a rough gamma-MnO 2 plating layer.
Example 1: the titanium-based gradient composite manganese dioxide anode plate of the embodiment (see figures 1-4);
The length of the titanium-coated aluminum conductive beam 1 is 1200mm, the width is 40mm, the height is 50mm, the thickness of a titanium layer of the titanium-coated aluminum conductive beam 1 is 2mm, one end of the titanium-coated aluminum conductive beam 1 is welded with a copper-aluminum composite conductive head 1a, the length of the copper-aluminum composite conductive head 1a is 100mm, the width is 36mm, the height is 46mm, the thickness of a titanium plate 3 is 4mm, the titanium-coated aluminum composite rod 4 is round, and the diameter of round rod aluminum is The thickness of the titanium layer of the titanium-coated aluminum composite rod 4 is 1.5mm, the long axis of the double-layer titanium mesh 5 is 10mm, the short axis is 5mm, and the thickness of the section is 1.0mm; the titanium rod 6 is a round rod, wherein the diameter of the round rod isThe thickness of the metal oxide intermediate layer I is 2 mu m, the thickness of the metal oxide intermediate layer II is 3 mu m, and the thickness of the composite manganese dioxide active layer is 0.4mm;
The metal oxide interlayer I is Sn-SbOx, the metal oxide interlayer II is Pt-Sn-SbOx/Sn-SbOx oxide interlayer, and the composite manganese dioxide active layer contains Ag-doped carbon fiber-beta-PbO 2 composite particles, sn-Ru-TaOx coated hollow glass beads and gamma-MnO 2;
The granularity of the carbon fiber is 1 mu m, the granularity of the Ag-carbon fiber-beta-PbO 2 doped composite particle is 10 mu m, and the granularity of the hollow glass bead is 10 mu m;
The molar ratio of Pt, sn and Sb in Pt-Sn-SbOx is 3:86:11, and the molar ratio of Sn and Sb in Sn-SbOx is 70:30;
the mass percentage of the composite manganese dioxide active layer is 100 percent, the composite particles doped with Ag-carbon fiber-beta-PbO 2 account for 1.0 percent, the hollow glass beads coated with Sn-Ru-TaOx account for 0.5 percent, W accounts for 0.1 percent, and the balance is gamma-MnO 2; the Ag-carbon fiber-beta-PbO 2 composite particles contain 0.5 mass percent of Ag, 0.1 mass percent of carbon fiber powder and the balance of beta-PbO 2; the molar ratio of Sn, ru and Ta in the Sn-Ru-TaOx coated hollow glass microsphere is 40:30:30, and the Sn-Ru-TaOx oxide accounts for 1.0% of the mass of the Sn-Ru-TaOx coated hollow glass microsphere;
the preparation method of the Ag-carbon fiber-beta-PbO 2 -doped composite particle comprises the following specific steps:
Taking stainless steel as an anode and a titanium mesh as a cathode, electrodepositing for 4 hours in an acidic lead nitrate composite plating solution to obtain an Ag-doped carbon fiber-beta-PbO 2 composite plating layer, stripping the Ag-doped carbon fiber-beta-PbO 2 composite plating layer, and performing ball milling to obtain Ag-doped carbon fiber-beta-PbO 2 composite particles; wherein the acidic lead nitrate composite plating solution contains 50g/L of lead nitrate, 0.5g/L of silver nitrate, 4g/L of thiourea and 4g/L of carbon fiber particles, and the pH value of the acidic lead nitrate composite plating solution is 0; the temperature of the electrodeposition is 60 ℃ and the current density is 6A/dm 2;
the preparation method of the Sn-Ru-TaOx coated hollow glass microsphere comprises the following specific steps:
1) Dissolving tin chloride, ruthenium chloride and tantalum chloride in concentrated hydrochloric acid, adding n-butanol solvent, and removing water by rotary evaporation to obtain tin ruthenium tantalum precursor liquid;
2) Calcining the hollow glass beads at 400 ℃ for 0.5h, immersing in a NaOH solution with the concentration of 5wt.% for 5min at the temperature of 60 ℃, immersing in a HF solution with the concentration of 0.5wt.% for 1min after washing with deionized water, carrying out deionized washing, and drying to obtain pretreated hollow glass beads;
3) Immersing the pretreated hollow glass beads in tin-Ru-TaOx precursor liquid for 5 minutes by ultrasonic immersion, drying at 100 ℃, roasting at 300 ℃ for 10 minutes, repeating the ultrasonic immersion and roasting processes for 6 times, and sintering at 480 ℃ for 1 hour to obtain Sn-Ru-TaOx coated hollow glass bead composite particles;
the preparation method of the titanium-based gradient composite manganese dioxide anode plate comprises the following specific steps:
(1) Immersing the aluminum bar into NaOH solution with the concentration of 5wt.% after degreasing and pickling, immersing for 1min at the temperature of 40 ℃, cleaning by deionized water, and immersing into HNO 3 solution with the concentration of 10wt.% for activation for 4min to obtain an activated aluminum bar; the inner wall of the titanium tube is treated by HF solution with the concentration of 1wt.% and is cleaned by deionized water to obtain a pretreated titanium tube; the pretreated titanium tube is sleeved outside the aluminum bar and is extruded, drawn and compounded, the titanium-aluminum clad composite bar is obtained by hot rolling at the temperature of 500 ℃, and the titanium-aluminum clad composite bar is welded with an aluminum-copper composite conductive head (pulse argon protection aluminum-aluminum welding) to obtain a titanium-aluminum clad conductive beam;
(2) Welding a titanium plate, a titanium-coated aluminum composite rod and a titanium rod to form a titanium-based oxide anode plate frame, immersing the titanium-based oxide anode plate frame in a NaOH solution with the concentration of 10wt.% for 10min at the temperature of 50 ℃, performing sand blasting surface treatment on the titanium-based oxide anode plate frame, performing heat treatment at the temperature of 400 ℃ for 0.2h, placing the titanium-based oxide anode plate frame in an oxalic acid solution with the concentration of 5wt.%, activating the oxalic acid solution at the temperature of 80 ℃ for 0.5h to obtain an activated titanium-based oxide anode plate frame, coating tin-antimony precursor liquid on the surface of the activated titanium-based oxide anode plate frame, drying the activated titanium-based oxide anode plate frame at the temperature of 100-120 ℃ for 8min, placing the activated titanium-based oxide anode plate frame at the temperature of 400 ℃ for 5min, repeating the 5 times of coating tin-antimony precursor liquid and sintering, and then placing the activated titanium-based oxide anode plate frame coated with a metal oxide Sn-SbOx intermediate layer for 1h in the sintering process at the temperature of 400 ℃;
(3) Immersing a drawn titanium mesh in NaOH solution with the concentration of 10wt.% at the temperature of 50 ℃ for 10min, carrying out sand blasting surface treatment on the titanium mesh, carrying out heat treatment at the temperature of 400 ℃ for 0.2h, then placing the titanium mesh in oxalic acid solution with the concentration of 5wt.% for 0.5h to obtain an activated titanium mesh, activating the surface of the activated titanium mesh to be coated with platinum-tin-antimony precursor liquid, drying the surface of the activated titanium mesh at the temperature of 100-120 ℃ for 8min, placing the surface of the activated titanium mesh at the temperature of 400 ℃ for sintering pretreatment for 5min, repeating the process of coating the platinum-tin-antimony precursor liquid and sintering for 5 times, and then placing the surface of the activated titanium mesh at the temperature of 400 ℃ for 1h to obtain the titanium mesh coated with Pt-Sn-SbOx; coating tin-antimony precursor liquid on the surface of the titanium mesh coated with Pt-Sn-SbOx, drying at 100-120 ℃ for 8min, placing at 400 ℃ for sintering pretreatment for 5min, repeating the process of coating tin-antimony precursor liquid and sintering for 5 times, and placing at 400 ℃ for sintering for 1h to obtain the titanium mesh coated with the Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer;
(4) Argon arc welding the titanium mesh coated with the Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer on the titanium-based oxide anode plate frame coated with the metal oxide Sn-SbOx intermediate layer to form a titanium-based oxide anode plate blank, wherein the titanium mesh coated with the Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer is positioned between adjacent titanium-clad aluminum composite rods; placing a titanium-based oxide anode plate blank serving as an anode and a titanium plate serving as a cathode in manganese nitrate composite electroplating solution, performing composite electrodeposition for 4 hours at the temperature of 80 ℃, cleaning with deionized water, and drying to obtain a titanium-based oxide anode plate; wherein the current density of the composite electrodeposition is 1A/dm 2, and the stirring speed is 50rpm; the manganese nitrate composite plating solution contains 40g/L manganese nitrate (Mn (NO 3)2), 10g/L nitric acid (HNO 3), 10g/L sodium tungstate (Na 2WO4), 10g/L Ag-doped carbon fiber-beta-PbO 2 composite particles and 4g/L Sn-Ru-TaOx coated hollow glass microspheres;
(5) Welding the top end of a titanium plate of a titanium-based oxide anode plate on the bottom end of a titanium-coated aluminum conductive beam, and mounting an insulator on the titanium-based oxide anode plate to obtain a titanium-based gradient composite manganese dioxide anode plate;
The titanium-based gradient composite manganese dioxide anode plate is used for non-ferrous metal (zinc) electrodeposition, the zinc ion concentration in a zinc electrolyte is 50g/L, the sulfuric acid concentration is 150g/L, the zinc electrodeposition is carried out at the temperature of 40 ℃ with the concentration of 600mg/L C1 - ions, the electrical efficiency of the gradient composite manganese dioxide anode plate is improved by 3% compared with that of a traditional lead-silver (0.75 wt.%) alloy anode plate, the tank voltage is reduced by 8%, the service life is prolonged by 1.5 times, and the cathode product zinc # 0 reaches more than 99%.
Example 2: the titanium-based gradient composite manganese dioxide anode plate of the embodiment (see figures 1-4);
The length of the titanium-coated aluminum conductive beam 1 is 1200mm, the width is 40mm, the height is 50mm, the thickness of a titanium layer of the titanium-coated aluminum conductive beam 1 is 2mm, one end of the titanium-coated aluminum conductive beam 1 is welded with a copper-aluminum composite conductive head 1a, the length of the copper-aluminum composite conductive head 1a is 100mm, the width is 36mm, the height is 46mm, the thickness of a titanium plate 3 is 4mm, the titanium-coated aluminum composite rod 4 is round, and the diameter of round rod aluminum is The thickness of the titanium layer of the titanium-coated aluminum composite rod 4 is 1.5mm, the long axis of the double-layer titanium mesh 5 is 10mm, the short axis is 5mm, and the thickness of the section is 1.5mm; the titanium rod 6 is a round rod, wherein the diameter of the round rod isThe thickness of the metal oxide intermediate layer I is 3 mu m, the thickness of the metal oxide intermediate layer II is 4 mu m, and the thickness of the composite manganese dioxide active layer is 1mm;
The metal oxide interlayer I is Sn-SbOx, the metal oxide interlayer II is Pt-Sn-SbOx/Sn-SbOx oxide interlayer, and the composite manganese dioxide active layer contains Ag-doped carbon fiber-beta-PbO 2 composite particles, sn-Ru-TaOx coated hollow glass beads and gamma-MnO 2; the granularity of the carbon fiber is 5 mu m, the granularity of the Ag-carbon fiber-beta-PbO 2 doped composite particle is 50 mu m, and the granularity of the hollow glass bead is 50 mu m; the molar ratio of Pt, sn and Sb in Pt-Sn-SbOx is 5:85:10, and the molar ratio of Sn and Sb in Sn-SbOx is 75:25;
Based on the mass percentage of 100% of the composite manganese dioxide active layer, 3% of Ag-carbon fiber-beta-PbO 2 composite particles, 0.5% of Sn-Ru-TaOx coated hollow glass beads, 1.0% of W and the balance of gamma-MnO 2; the Ag-carbon fiber-beta-PbO 2 composite particles contain 3% of Ag by mass, 0.5% of carbon fiber powder by mass and the balance of beta-PbO 2 by mass; the molar ratio of Sn, ru and Ta in the Sn-Ru-TaOx coated hollow glass microsphere is 45:40:15, and the Sn-Ru-TaOx oxide accounts for 2% of the mass of the Sn-Ru-TaOx coated hollow glass microsphere;
the preparation method of the Ag-carbon fiber-beta-PbO 2 -doped composite particle comprises the following specific steps:
Taking stainless steel as an anode and a titanium mesh as a cathode, electrodepositing for 6 hours in an acidic lead nitrate composite plating solution to obtain an Ag-doped carbon fiber-beta-PbO 2 composite plating layer, stripping the Ag-doped carbon fiber-beta-PbO 2 composite plating layer, and then ball milling until the average grain diameter is 10 mu m to obtain Ag-doped carbon fiber-beta-PbO 2 composite particles; wherein the acidic lead nitrate composite plating solution contains 150g/L of lead nitrate, 10g/L of silver nitrate, 16g/L of thiourea and 12g/L of carbon fiber particles, and the pH value of the acidic lead nitrate composite plating solution is 1; the temperature of the electrodeposition is 75 ℃, and the current density is 10A/dm 2;
the preparation method of the Sn-Ru-TaOx coated hollow glass microsphere comprises the following specific steps:
1) Dissolving tin chloride, ruthenium chloride and tantalum chloride in concentrated hydrochloric acid, adding n-butanol solvent, and removing water by rotary evaporation to obtain tin ruthenium tantalum precursor liquid;
2) Calcining the hollow glass beads at 500 ℃ for 1.5 hours, immersing in an NaOH solution with the concentration of 8wt.% for 20min at the temperature of 70 ℃, immersing in an HF solution with the concentration of 1.2wt.% for 3min after washing with deionized water, carrying out deionized washing, and drying to obtain pretreated hollow glass beads;
3) Immersing the pretreated hollow glass beads in tin-Ru-TaOx precursor liquid for 8min, drying at 120 ℃, roasting at 500 ℃ for 15min, repeating the ultrasonic immersing and roasting process for 10 times, and sintering at 480 ℃ for 2h to obtain Sn-Ru-TaOx coated hollow glass bead composite particles;
the preparation method of the titanium-based gradient composite manganese dioxide anode plate comprises the following specific steps:
(1) Immersing an aluminum bar in NaOH solution with the concentration of 8wt.% after degreasing and pickling, immersing for 3min at the temperature of 60 ℃, cleaning by deionized water, and immersing in HNO 3 solution with the concentration of 20wt.% for activating for 6min to obtain an activated aluminum bar; the inner wall of the titanium tube is treated by HF solution with the concentration of 5wt.% and is cleaned by deionized water to obtain a pretreated titanium tube; the pretreated titanium tube is sleeved outside the aluminum bar and is extruded, drawn and compounded, the titanium-aluminum clad composite bar is obtained by hot rolling at the temperature of 600 ℃, and the titanium-aluminum clad composite bar is welded with an aluminum-copper composite conductive head (pulse argon protection aluminum-aluminum welding) to obtain a titanium-aluminum clad conductive beam;
(2) Welding a titanium plate, a titanium-coated aluminum composite rod and a titanium rod to form a titanium-based oxide anode plate frame, immersing the titanium-based oxide anode plate frame in a NaOH solution with the concentration of 15wt.% for 20min at the temperature of 60 ℃, performing heat treatment for 1.0h at the temperature of 600 ℃ after the titanium-based oxide anode plate frame is subjected to sand blasting surface treatment, then placing the titanium-based oxide anode plate frame in an oxalic acid solution with the concentration of 20wt.% for 1.0h at the temperature of 100 ℃ to obtain an activated titanium-based oxide anode plate frame, coating tin-antimony precursor liquid on the surface of the activated titanium-based oxide anode plate frame, drying the activated titanium-based oxide anode plate frame at the temperature of 120 ℃ for 10min, placing the activated titanium-based oxide anode plate frame at the temperature of 600 ℃ for 8min, repeating 7 times of coating tin-antimony precursor liquid and sintering processes, and then placing the activated titanium-based oxide anode plate frame coated with a metal oxide Sn-SbOx interlayer for 1.5h at the temperature of 550 ℃;
(3) Immersing a drawn titanium mesh in a NaOH solution with the concentration of 15wt.% at the temperature of 70 ℃ for 20min, carrying out sand blasting surface treatment on the titanium mesh, carrying out heat treatment at the temperature of 600 ℃ for 1.0h, then placing the titanium mesh in an oxalic acid solution with the concentration of 20wt.% for 1.0h to obtain an activated titanium mesh, activating the surface of the activated titanium mesh to be coated with platinum-tin-antimony precursor liquid, drying the surface of the activated titanium mesh at the temperature of 100 ℃ for 10min, placing the surface of the activated titanium mesh at the temperature of 600 ℃ for sintering pretreatment for 8min, repeating 7 times of coating the platinum-tin-antimony precursor liquid and sintering process, and then placing the surface of the activated titanium mesh at the temperature of 550 ℃ for 1.5h to obtain the titanium mesh coated with Pt-Sn-SbOx; coating tin-antimony precursor liquid on the surface of the titanium mesh coated with Pt-Sn-SbOx, drying at 100 ℃ for 10min, placing at 600 ℃ for sintering pretreatment for 8min, repeating 7 times of coating tin-antimony precursor liquid and sintering process, and placing at 500 ℃ for sintering for 1.5h to obtain the titanium mesh coated with the Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer;
(4) Argon arc welding the titanium mesh coated with the Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer on the titanium-based oxide anode plate frame coated with the metal oxide Sn-SbOx intermediate layer to form a titanium-based oxide anode plate blank, wherein the titanium mesh coated with the Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer is positioned between adjacent titanium-clad aluminum composite rods; placing a titanium-based oxide anode plate blank serving as an anode and a titanium plate serving as a cathode in manganese nitrate composite electroplating solution, performing composite electrodeposition for 10 hours at the temperature of 90 ℃, cleaning with deionized water, and drying to obtain a titanium-based oxide anode plate; wherein the current density of the composite electrodeposition is 3A/dm 2, and the stirring speed is 150rpm; the manganese nitrate composite plating solution contains 80g/L manganese nitrate (Mn (NO 3)2), 20g/L nitric acid (HNO 3), 30g/L sodium tungstate (Na 2WO4), 20g/L Ag-doped carbon fiber-beta-PbO 2 composite particles and 20g/L Sn-Ru-TaOx coated hollow glass microspheres;
(5) Welding the top end of a titanium plate of a titanium-based oxide anode plate on the bottom end of a titanium-coated aluminum conductive beam, and mounting an insulator on the titanium-based oxide anode plate to obtain a titanium-based gradient composite manganese dioxide anode plate;
The titanium-based gradient composite manganese dioxide anode plate is used for non-ferrous metal (zinc) electrodeposition, the zinc ion concentration in a zinc electrolyte is 50g/L, the sulfuric acid concentration is 150g/L, the zinc electrodeposition is carried out at the temperature of 40 ℃ with the concentration of 600mg/L C1 - ions, the electrical efficiency of the gradient composite manganese dioxide anode plate is improved by 4% compared with that of a traditional lead-silver (0.75 wt.%) alloy anode plate, the tank voltage is reduced by 18%, the service life is prolonged by 2 times, and the cathode product zinc No. 0 reaches more than 99%.
Example 3: the titanium-based gradient composite manganese dioxide anode plate of the embodiment (see figures 1-4);
The length of the titanium-coated aluminum conductive beam 1 is 1300mm, the width is 20mm, the height is 40mm, the thickness of a titanium layer of the titanium-coated aluminum conductive beam 1 is 1mm, one end of the titanium-coated aluminum conductive beam 1 is welded with a copper-aluminum composite conductive head 1a, the length of the copper-aluminum composite conductive head 1a is 100mm, the width is 18mm, the height is 38mm, the thickness of a titanium plate 3 is 3mm, the titanium-coated aluminum composite rod 4 is square, wherein the section length of square aluminum is 4mm, the width is 1mm, the thickness of the titanium layer of the titanium-coated aluminum composite rod 4 is 0.5mm, the long axis of a double-layer titanium mesh 5 is 3mm, the short axis is 1mm, and the section thickness is 0.5mm; the titanium rod 6 is a square rod, wherein the section of Fang Xingbang is 4mm long and 3mm wide, the thickness of the metal oxide intermediate layer I is 1 mu m, the thickness of the metal oxide intermediate layer II is 2 mu m, and the thickness of the composite manganese dioxide active layer is 0.3mm;
The metal oxide intermediate layer I is Sn-SbOx, the metal oxide intermediate layer II is Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer, and the composite manganese dioxide active layer contains Ag-carbon fiber-beta-PbO 2 doped composite particles, sn-Ru-TaOx coated hollow glass beads and gamma-MnO 2; the granularity of the carbon fiber is 1 mu m, the granularity of the Ag-carbon fiber-beta-PbO 2 doped composite particle is 10 mu m, and the granularity of the hollow glass bead is 10 mu m; the molar ratio of Pt, ti, sn and Sb in Pd-Ti-Sn-SbOx is 3:5:75:17, and the molar ratio of Sn and Sb in Sn-SbOx is 70:30;
The mass percentage of the composite manganese dioxide active layer is 100 percent, the composite particles doped with Ag-carbon fiber-beta-PbO 2 account for 1 percent, the Sn-Ru-TaOx coated hollow glass beads account for 0.5 percent, the W accounts for 0.1 percent, and the balance is gamma-MnO 2; the Ag-carbon fiber-beta-PbO 2 composite particles contain 0.5 mass percent of Ag, 0.1 mass percent of carbon fiber powder and the balance of beta-PbO 2; the molar ratio of Sn, ru and Ta in the Sn-Ru-TaOx coated hollow glass microsphere is 40:30:30, and the Sn-Ru-TaOx oxide accounts for 1% of the mass of the Sn-Ru-TaOx coated hollow glass microsphere;
the preparation method of the Ag-carbon fiber-beta-PbO 2 -doped composite particle comprises the following specific steps:
Taking stainless steel as an anode and a titanium mesh as a cathode, electrodepositing for 4 hours in an acidic lead nitrate composite plating solution to obtain an Ag-doped carbon fiber-beta-PbO 2 composite plating layer, stripping the Ag-doped carbon fiber-beta-PbO 2 composite plating layer, and performing ball milling to obtain Ag-doped carbon fiber-beta-PbO 2 composite particles; wherein the acidic lead nitrate composite plating solution contains 50g/L of lead nitrate, 0.5g/L of silver nitrate, 4g/L of thiourea and 4g/L of carbon fiber particles, and the pH value of the acidic lead nitrate composite plating solution is; the temperature of the electrodeposition is 60 ℃ and the current density is 6A/dm 2;
the preparation method of the Sn-Ru-TaOx coated hollow glass microsphere comprises the following specific steps:
1) Dissolving tin chloride, ruthenium chloride and tantalum chloride in concentrated hydrochloric acid, adding n-butanol solvent, and removing water by rotary evaporation to obtain tin ruthenium tantalum precursor liquid;
2) Calcining the hollow glass beads at 400 ℃ for 0.5h, immersing in a NaOH solution with the concentration of 5wt.% for 5min at the temperature of 60 ℃, immersing in a HF solution with the concentration of 0.5wt.% for 1min after washing with deionized water, carrying out deionized washing, and drying to obtain pretreated hollow glass beads;
3) Immersing the pretreated hollow glass beads in tin-Ru-TaOx precursor liquid for 5 minutes by ultrasonic immersion, drying at 100 ℃, roasting at 300 ℃ for 10 minutes, repeating the ultrasonic immersion and roasting processes for 6 times, and sintering at 480 ℃ for 1 hour to obtain Sn-Ru-TaOx coated hollow glass bead composite particles;
the preparation method of the titanium-based gradient composite manganese dioxide anode plate comprises the following specific steps:
(1) Immersing the aluminum bar into NaOH solution with the concentration of 5wt.% after degreasing and pickling, immersing for 1min at the temperature of 40 ℃, cleaning by deionized water, and immersing into HNO 3 solution with the concentration of 10wt.% for activation for 4min to obtain an activated aluminum bar; the inner wall of the titanium tube is treated by HF solution with the concentration of 1wt.% and is cleaned by deionized water to obtain a pretreated titanium tube; the pretreated titanium tube is sleeved outside the aluminum bar and is extruded, drawn and compounded, the titanium-aluminum clad composite bar is obtained by hot rolling at the temperature of 500 ℃, and the titanium-aluminum clad composite bar is welded with an aluminum-copper composite conductive head (pulse argon protection aluminum-aluminum welding) to obtain a titanium-aluminum clad conductive beam;
(2) Welding a titanium plate, a titanium-coated aluminum composite rod and a titanium rod to form a titanium-based oxide anode plate frame, immersing the titanium-based oxide anode plate frame in a NaOH solution with the concentration of 10wt.% for 10min at the temperature of 50 ℃, performing sand blasting surface treatment on the titanium-based oxide anode plate frame, performing heat treatment for 0.2h at the temperature of 400 ℃, placing the titanium-based oxide anode plate frame in an oxalic acid solution with the concentration of 5wt.%, activating for 0.5h at the temperature of 80 ℃ to obtain an activated titanium-based oxide anode plate frame, coating tin-antimony precursor liquid on the surface of the activated titanium-based oxide anode plate frame, drying for 5min at the temperature of 120 ℃, placing the activated titanium-based oxide anode plate frame at the temperature of 400 ℃ for 5min for sintering pretreatment, repeating the 3 times of coating tin-antimony precursor liquid and sintering process, and then placing the activated titanium-based oxide anode plate frame coated with a metal oxide Sn-SbOx interlayer for 1h for sintering at the temperature of 400 ℃;
(3) Immersing a drawn titanium mesh in NaOH solution with the concentration of 10wt.% at the temperature of 50 ℃ for 10min, carrying out sand blasting surface treatment on the titanium mesh, carrying out heat treatment at the temperature of 400 ℃ for 0.2h, then placing the titanium mesh in oxalic acid solution with the concentration of 5wt.% for 0.5h to obtain an activated titanium mesh, coating palladium titanium tin antimony precursor liquid on the surface of the activated titanium mesh, drying the activated titanium mesh at the temperature of 100-120 ℃ for 8min, placing the activated titanium mesh at the temperature of 400 ℃ for sintering pretreatment for 5min, repeating the 3 times of coating palladium titanium tin antimony precursor liquid and sintering process, and then placing the activated titanium mesh at the temperature of 400 ℃ for 1h to obtain the titanium mesh coated with Pd-Ti-Sn-SbOx; coating tin-antimony precursor liquid on the surface of the titanium mesh coated with Pd-Ti-Sn-SbOx, drying at 100-120 ℃ for 8min, placing the titanium mesh at 400 ℃ for sintering pretreatment for 5min, repeating the process of coating tin-antimony precursor liquid and sintering for 3 times, and placing the titanium mesh at 400 ℃ for sintering for 1.0h to obtain the titanium mesh coated with the Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer;
(4) Argon arc welding the titanium mesh coated with the Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer on the titanium-based oxide anode plate frame coated with the metal oxide Sn-SbOx intermediate layer to form a titanium-based oxide anode plate blank, wherein the titanium mesh coated with the Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer is positioned between adjacent titanium-clad aluminum composite rods; placing a titanium-based oxide anode plate blank serving as an anode and a titanium plate serving as a cathode in manganese nitrate composite electroplating solution, performing composite electrodeposition for 4 hours at the temperature of 80 ℃, cleaning with deionized water, and drying to obtain a titanium-based oxide anode plate; wherein the current density of the composite electrodeposition is 1A/dm 2, and the stirring speed is 50rpm; the manganese nitrate composite plating solution contains 20g/L manganese nitrate (Mn (NO 3)2), 10g/L nitric acid (HNO 3), 10g/L sodium tungstate (Na 2WO4), 10g/L Ag-doped carbon fiber-beta-PbO 2 composite particles and 4g/LSn-Ru-TaOx coated hollow glass microspheres;
(5) Welding the top end of a titanium plate of a titanium-based oxide anode plate on the bottom end of a titanium-coated aluminum conductive beam, and mounting an insulator on the titanium-based oxide anode plate to obtain a titanium-based gradient composite manganese dioxide anode plate;
The titanium-based gradient composite manganese dioxide anode plate is used for nonferrous metal (copper) electrodeposition, the copper ion concentration in a copper electrolyte is 45g/L, the sulfuric acid concentration is 180g/L,100mg/L C < 1 > - - ions are subjected to copper electrodeposition at the temperature of 50 ℃, the electrical efficiency of the gradient composite manganese dioxide anode plate is improved by 3% compared with that of a traditional lead-calcium (0.07 wt.%) -tin (1.25 wt.%) alloy anode plate, the tank voltage is reduced by 10%, the service life is prolonged by 1 time, and the 0# zinc of a cathode product reaches more than 99%.
Example 4: the titanium-based gradient composite manganese dioxide anode plate of the embodiment (see figures 1-4);
The length of the titanium-coated aluminum conductive beam 1 is 1300mm, the width is 50mm, the height is 60mm, the thickness of a titanium layer of the titanium-coated aluminum conductive beam 1 is 3mm, one end of the titanium-coated aluminum conductive beam 1 is welded with a copper-aluminum composite conductive head 1a, the length of the copper-aluminum composite conductive head 1a is 120mm, the width is 44mm, the height is 54mm, the thickness of a titanium plate 3 is 2mm, the titanium-coated aluminum composite rod 4 is square, wherein the section length of square aluminum is 10mm, the width is 4mm, the thickness of the titanium layer of the titanium-coated aluminum composite rod 4 is 2mm, the long axis of a double-layer titanium mesh 5 is 16mm, the short axis is 6mm, and the section thickness is 0.7mm; the titanium rod 6 is a square rod, wherein the section of Fang Xingbang is 10mm long and 5mm wide, the thickness of the metal oxide intermediate layer I is 5 mu m, the thickness of the metal oxide intermediate layer II is 5 mu m, and the thickness of the composite manganese dioxide active layer is 2mm;
The metal oxide intermediate layer I is Sn-SbOx, the metal oxide intermediate layer II is Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer, and the composite manganese dioxide active layer contains Ag-carbon fiber-beta-PbO 2 doped composite particles, sn-Ru-TaOx coated hollow glass beads and gamma-MnO 2; the granularity of the carbon fiber is 10 mu m, the granularity of the Ag-carbon fiber-beta-PbO 2 doped composite particle is 100 mu m, and the granularity of the hollow glass bead is 100 mu m; the molar ratio of Pt, sn and Sb in Pd-Ti-Sn-SbOx is 3:5:75:17, and the molar ratio of Sn and Sb in Sn-SbOx is 70:30;
The mass percentage of the composite manganese dioxide active layer is 100%, the composite particles doped with Ag-carbon fiber-beta-PbO 2 account for 6%, the hollow glass beads coated with Sn-Ru-TaOx account for 4%, W accounts for 1.8%, and the balance is gamma-MnO 2; the Ag-carbon fiber-beta-PbO 2 composite particles contain 5 mass percent of Ag, 1 mass percent of carbon fiber powder and the balance of beta-PbO 2; the molar ratio of Sn, ru and Ta in the Sn-Ru-TaOx coated hollow glass microsphere is 1:80:19, and the Sn-Ru-TaOx oxide accounts for 8% of the mass of the Sn-Ru-TaOx coated hollow glass microsphere;
the preparation method of the Ag-carbon fiber-beta-PbO 2 -doped composite particle comprises the following specific steps:
Taking stainless steel as an anode and a titanium mesh as a cathode, electrodepositing for 8 hours in an acidic lead nitrate composite plating solution to obtain an Ag-doped carbon fiber-beta-PbO 2 composite plating layer, stripping the Ag-doped carbon fiber-beta-PbO 2 composite plating layer, and performing ball milling to obtain Ag-doped carbon fiber-beta-PbO 2 composite particles; wherein the acidic lead nitrate composite plating solution contains 150g/L of lead nitrate, 20g/L of silver nitrate, 20g/L of thiourea and 20g/L of carbon fiber particles, and the pH value of the acidic lead nitrate composite plating solution is 2; the temperature of the electrodeposition is 90 ℃ and the current density is 12A/dm 2;
the preparation method of the Sn-Ru-TaOx coated hollow glass microsphere comprises the following specific steps:
1) Dissolving tin chloride, ruthenium chloride and tantalum chloride in concentrated hydrochloric acid, adding n-butanol solvent, and removing water by rotary evaporation to obtain tin ruthenium tantalum precursor liquid;
2) Calcining the hollow glass beads at 600 ℃ for 2 hours, immersing the hollow glass beads in a 10wt.% NaOH solution, treating the hollow glass beads at 90 ℃ for 40 minutes, immersing the hollow glass beads in a 2wt.% HF solution for 5 minutes after washing with deionized water, carrying out deionized washing, and drying to obtain pretreated hollow glass beads;
3) Immersing the pretreated hollow glass beads in tin-Ru-TaOx precursor liquid for 10min, drying at 100 ℃, roasting at 560 ℃ for 20min, repeating the ultrasonic immersing and roasting processes for 12 times, and sintering at 480 ℃ for 2h to obtain Sn-Ru-TaOx coated hollow glass bead composite particles;
the preparation method of the titanium-based gradient composite manganese dioxide anode plate comprises the following specific steps:
(1) Immersing the aluminum bar into a NaOH solution with the concentration of 15wt.% after degreasing and pickling, immersing for 5min at the temperature of 70 ℃, cleaning by deionized water, and immersing into a HNO 3 solution with the concentration of 40wt.% for activating for 8min to obtain an activated aluminum bar; the inner wall of the titanium tube is treated by HF solution with the concentration of 10wt.% and is cleaned by deionized water to obtain a pretreated titanium tube; the pretreated titanium tube is sleeved outside the aluminum bar and is extruded, drawn and compounded, the titanium-aluminum clad composite bar is obtained by hot rolling at the temperature of 700 ℃, and the titanium-aluminum clad composite bar is welded with an aluminum-copper composite conductive head (pulse argon protection aluminum-aluminum welding) to obtain a titanium-aluminum clad conductive beam;
(2) Welding a titanium plate, a titanium-coated aluminum composite rod and a titanium rod to form a titanium-based oxide anode plate frame, immersing the titanium-based oxide anode plate frame in a NaOH solution with the concentration of 20wt.% for 30min at the temperature of 80 ℃, performing heat treatment for 1.5h at the temperature of 700 ℃ after performing sand blasting surface treatment on the titanium-based oxide anode plate frame, then placing the titanium-based oxide anode plate frame in an oxalic acid solution with the concentration of 30wt.% for 2.0h at the temperature of 100 ℃ to obtain an activated titanium-based oxide anode plate frame, coating tin-antimony precursor liquid on the surface of the activated titanium-based oxide anode plate frame, drying the activated titanium-based oxide anode plate frame at the temperature of 110 ℃ for 8min, placing the activated titanium-based oxide anode plate frame at the temperature of 700 ℃ for 10min for sintering pretreatment, repeating 10 times of coating tin-antimony precursor liquid and sintering process, and then placing the activated titanium-based oxide anode plate frame coated with a metal oxide Sn-SbOx interlayer for 2h at the temperature of 600 ℃;
(3) Immersing a drawn titanium mesh in a NaOH solution with the concentration of 20wt.% at the temperature of 80 ℃ for 30min, carrying out sand blasting surface treatment on the titanium mesh, carrying out heat treatment at the temperature of 700 ℃ for 1.5h, then placing the titanium mesh in an oxalic acid solution with the concentration of 30wt.% for 2.0h to obtain an activated titanium mesh, coating palladium titanium tin antimony precursor liquid on the surface of the activated titanium mesh, drying the activated titanium mesh at the temperature of 120 ℃ for 8min, placing the activated titanium mesh at the temperature of 600 ℃ for sintering pretreatment for 10min, repeating 10 times of coating palladium titanium tin antimony precursor liquid and sintering process, and then placing the activated titanium mesh at the temperature of 600 ℃ for sintering for 2h to obtain the titanium mesh coated with Pd-Ti-Sn-SbOx; coating tin-antimony precursor liquid on the surface of the titanium mesh coated with Pd-Ti-Sn-SbOx, drying at 120 ℃ for 8min, placing at 600 ℃ for sintering pretreatment for 10min, repeating 10 times of coating tin-antimony precursor liquid and sintering process, and placing at 600 ℃ for sintering for 2h to obtain the titanium mesh coated with Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer;
(4) Argon arc welding the titanium mesh coated with the Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer on the titanium-based oxide anode plate frame coated with the metal oxide Sn-SbOx intermediate layer to form a titanium-based oxide anode plate blank, wherein the titanium mesh coated with the Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer is positioned between adjacent titanium-clad aluminum composite rods; placing a titanium-based oxide anode plate blank serving as an anode and a titanium plate serving as a cathode in manganese nitrate composite electroplating solution, performing composite electrodeposition for 20 hours at the temperature of 100 ℃, cleaning with deionized water, and drying to obtain a titanium-based oxide anode plate; wherein the current density of the composite electrodeposition is 5A/dm 2, and the stirring speed is 300rpm; the manganese nitrate composite plating solution contains 100g/L manganese nitrate (Mn (NO 3)2), 30g/L nitric acid (HNO 3), 40g/L sodium tungstate (Na 2WO4), 30g/L Ag-doped carbon fiber-beta-PbO 2 composite particles and 30g/L Sn-Ru-TaOx coated hollow glass microspheres;
(5) Welding the top end of a titanium plate of a titanium-based oxide anode plate on the bottom end of a titanium-coated aluminum conductive beam, and mounting an insulator on the titanium-based oxide anode plate to obtain a titanium-based gradient composite manganese dioxide anode plate;
The titanium-based gradient composite manganese dioxide anode plate is used for nonferrous metal (copper) electrodeposition, the copper ion concentration in a copper electrolyte is 45g/L, the sulfuric acid concentration is 180g/L,100mg/L C < 1 > - - ions are subjected to copper electrodeposition at the temperature of 50 ℃, the electrical efficiency of the gradient composite manganese dioxide anode plate is improved by 3% compared with that of a traditional lead-calcium (0.07 wt.%) -tin (1.25 wt.%) alloy anode plate, the tank voltage is reduced by 15%, the service life is prolonged by 2 times, and the 0# zinc of a cathode product reaches more than 99%.
While the specific embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes may be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (7)
1. A titanium-based gradient composite manganese dioxide anode plate is characterized in that: the titanium-coated aluminum conductive beam comprises a titanium-coated aluminum conductive beam (1) and a titanium-based oxide anode plate (2), wherein the titanium-based oxide anode plate (2) is fixedly arranged at the bottom end of the titanium-coated aluminum conductive beam (1), and an insulator (7) is arranged on the titanium-based oxide anode plate (2);
The titanium-based oxide anode plate (2) comprises a titanium plate (3), titanium-coated aluminum composite rods (4), double-layer titanium nets (5) and titanium rods (6), wherein the top ends of the titanium plate (3) are fixedly connected with the bottom ends of titanium-coated aluminum conductive beams (1), the titanium-coated aluminum composite rods (4) are vertically arranged at the bottom ends of the titanium plate (3), the titanium rods (6) are arranged at the bottom ends of the titanium-coated aluminum composite rods (4), the titanium plate (3), the titanium-coated aluminum composite rods (4) and the titanium rods (6) form a titanium-based oxide anode plate frame, the double-layer titanium nets (5) are arranged between the adjacent titanium-coated aluminum composite rods (4), the top ends of the double-layer titanium nets (5) are fixedly connected with the titanium plate (3), and the bottom ends of the double-layer titanium nets (5) are fixedly connected with the titanium rods (6); the titanium surface of the titanium-based oxide anode plate frame is sequentially coated with a metal oxide intermediate layer I and a composite manganese dioxide active layer, and the titanium surface of the double-layer titanium mesh (5) is sequentially coated with a metal oxide intermediate layer II and a composite manganese dioxide active layer;
The metal oxide intermediate layer I is Sn-SbOx, the metal oxide intermediate layer II is a Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer or a Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer, and the composite manganese dioxide active layer contains Ag-carbon fiber-beta-PbO 2 doped composite particles, sn-Ru-TaOx coated hollow glass beads and gamma-MnO 2;
The mol ratio of Pt, sn and Sb in the Pt-Sn-SbOx is 1-7:80-87:6-19, the mol ratio of Pd, ti, sn and Sb in the Pd-Ti-Sn-SbOx is 1-5:3-8:70-85:2-24, and the mol ratio of Sn and Sb in the Sn-SbOx is 70-80:20-30;
The mass percentage of the composite manganese dioxide active layer is 100 percent, the composite particles of the Ag-doped carbon fiber-beta-PbO 2 account for 1 to 6 percent, the Sn-Ru-TaOx coated hollow glass beads account for 0.5 to 4 percent, the W accounts for 0.05 to 2 percent, and the balance is gamma-MnO 2; the Ag-carbon fiber-beta-PbO 2 composite particles comprise 0.5-5% of Ag, 0.1-1% of carbon fiber powder and the balance of beta-PbO 2; the molar ratio of Sn, ru and Ta in the Sn-Ru-TaOx coated hollow glass microsphere is 40-50:30-42:8-30, and the Sn-Ru-TaOx oxide accounts for 1-8% of the mass of the Sn-Ru-TaOx coated hollow glass microsphere.
2. The titanium-based gradient composite manganese dioxide anode plate of claim 1, wherein: the thickness of the titanium layer of the titanium-coated aluminum conductive beam (1) is 1-3 mm, one end of the titanium-coated aluminum conductive beam (1) is welded with a copper-aluminum composite conductive head, the thickness of a titanium plate (3) is 3-5 mm, the thickness of the titanium layer of the titanium-coated aluminum composite rod (4) is 0.5-2 mm, the long axis of a double-layer titanium mesh of the double-layer titanium mesh (5) is 3-16 mm, the short axis is 1-6 mm, and the section thickness is 0.5-3 mm; the thicknesses of the metal oxide intermediate layer I and the metal oxide intermediate layer II are 1-5 mu m, and the thickness of the composite manganese dioxide active layer is 0.3-2 mm.
3. The titanium-based gradient composite manganese dioxide anode plate of claim 1, wherein: the granularity of the carbon fiber is 1-10 mu m, the granularity of the Ag-carbon fiber-beta-PbO 2 doped composite particle is 10-100 mu m, and the granularity of the hollow glass bead is 10-100 mu m.
4. The titanium-based gradient composite manganese dioxide anode plate of claim 1, wherein: the preparation method of the Ag-carbon fiber-beta-PbO 2 -doped composite particle comprises the following specific steps:
Electrodepositing stainless steel serving as an anode and a titanium mesh serving as a cathode in an acidic lead nitrate composite plating solution for 4-8 hours to obtain an Ag-doped carbon fiber-beta-PbO 2 composite plating layer, stripping the Ag-doped carbon fiber-beta-PbO 2 composite plating layer, and performing ball milling to obtain Ag-doped carbon fiber-beta-PbO 2 composite particles; the acidic lead nitrate composite plating solution contains 50-200 g/L of lead nitrate, 0.5-20 g/L of silver nitrate, 4-20 g/L of thiourea and 4-20 g/L of carbon fiber particles, and the pH value of the acidic lead nitrate composite plating solution is 0-2; the temperature of the electrodeposition is 60-90 ℃, and the current density is 6-12A/dm 2.
5. The titanium-based gradient composite manganese dioxide anode plate of claim 1, wherein: the preparation method of the Sn-Ru-TaOx coated hollow glass microsphere comprises the following specific steps:
1) Dissolving tin chloride, ruthenium chloride and tantalum chloride in concentrated hydrochloric acid, adding n-butanol solvent, and removing water by rotary evaporation to obtain tin ruthenium tantalum precursor liquid;
2) Calcining the hollow glass beads at 400-600 ℃ for 0.5-2 h, immersing in a NaOH solution with the concentration of 5-10 wt.%, treating at 60-90 ℃ for 5-40 min, immersing in an HF solution with the concentration of 0.5-2 wt.% for 1-5 min after washing with deionized water, performing deionized washing, and drying to obtain pretreated hollow glass beads;
3) Immersing the pretreated hollow glass beads in tin-ruthenium-tantalum precursor liquid for 5-10 min, drying, roasting at 300-560 ℃ for 10-20 min, repeating the ultrasonic immersing and roasting processes for 6-12 times, and sintering at 400-480 ℃ for 1-2 h to obtain the Sn-Ru-TaOx coated hollow glass bead composite particles.
6. The method for preparing the titanium-based gradient composite manganese dioxide anode plate according to any one of claims 1 to 5, which is characterized in that: the method comprises the following specific steps:
(1) Immersing the aluminum bar into NaOH solution for 1-5 min after degreasing and pickling, cleaning by deionized water, and immersing into HNO 3 solution for activation for 4-8 min to obtain an activated aluminum bar; the inner wall of the titanium tube is treated by HF solution, and is cleaned by deionized water to obtain a pretreated titanium tube; the pretreated titanium tube is sleeved outside the aluminum rod and is extruded, drawn and compounded, the titanium-coated aluminum composite rod is obtained through hot rolling, and the titanium-coated aluminum composite rod and the aluminum-copper composite conductive head are welded to obtain a titanium-coated aluminum conductive beam;
(2) Welding a titanium plate, a titanium-coated aluminum composite rod and a titanium rod to form a titanium-based oxide anode plate frame, immersing the titanium-based oxide anode plate frame in a NaOH solution for 10-30 min, performing heat treatment on the titanium-based oxide anode plate frame after sand blasting surface treatment, then placing the titanium-based oxide anode plate frame in an oxalic acid solution for activating for 0.5-2.0 h to obtain an activated titanium-based oxide anode plate frame, coating tin-antimony precursor liquid on the surface of the activated titanium-based oxide anode plate frame, drying, performing sintering pretreatment for 5-10 min, repeating the steps of coating tin-antimony precursor liquid and sintering for 3-10 times, and then placing the titanium-based oxide anode plate frame coated with a metal oxide intermediate layer at the temperature of 400-600 ℃ for sintering for 1-2 h to obtain the titanium-based oxide anode plate frame coated with the metal oxide intermediate layer;
(3) Immersing a drawn titanium mesh in a NaOH solution for 10-30 min, performing heat treatment after performing sand blasting surface treatment on the titanium mesh, then placing the titanium mesh in an oxalic acid solution for activation for 0.5-2.0 h to obtain an activated titanium mesh, coating platinum tin antimony precursor liquid or palladium titanium tin antimony precursor liquid on the surface of the activated titanium mesh, drying, performing sintering pretreatment for 5-10 min, repeating the coating and sintering processes for 3-10 times, and then placing the titanium mesh at 400-600 ℃ for sintering for 1-2 h to obtain a titanium mesh coated with Pt-Sn-SbOx or Pd-Ti-Sn-Sb; coating tin-antimony precursor liquid on the surface of the titanium mesh coated with Pt-Sn-SbOx or Pd-Ti-Sn-Sb, drying, then sintering and pre-treating for 5-10 min, repeating the steps of coating tin-antimony precursor liquid and sintering for 3-5 times, and then sintering for 1-2 h at the temperature of 400-600 ℃ to obtain the titanium mesh coated with the Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer or Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer;
(4) Welding a titanium mesh coated with a Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer or a Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer on a titanium-based oxide anode plate frame coated with a metal oxide intermediate layer to form a titanium-based oxide anode plate blank, wherein the titanium mesh coated with the Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer or the Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer is positioned between adjacent titanium-clad aluminum composite rods; placing a titanium-based oxide anode plate blank serving as an anode and a titanium plate serving as a cathode in a manganese nitrate composite electroplating solution for composite electrodeposition, cleaning with deionized water, and drying to obtain a titanium-based oxide anode plate;
(5) And welding the top end of a titanium plate of the titanium-based oxide anode plate to the bottom end of a titanium-coated aluminum conductive beam, and mounting an insulator on the titanium-based oxide anode plate to obtain the titanium-based gradient composite manganese dioxide anode plate.
7. The method for preparing the titanium-based gradient composite manganese dioxide anode plate according to claim 6, wherein the method comprises the following steps: the method comprises the steps of (1) 5-10wt.% of NaOH solution, 40-70 ℃ of NaOH solution soaking temperature, 10-40 wt.% of HNO 3 solution, 1-10wt.% of HF solution, 500-700 ℃ of hot rolling temperature and pulse argon protection aluminum-aluminum welding;
the concentration of the NaOH solution is 10-20wt%, the soaking temperature of the NaOH solution is 50-80 ℃, the heat treatment temperature is 400-700 ℃, the heat treatment time is 0.2-1.5 h, the concentration of the oxalic acid solution is 5-30wt%, the activation temperature is 80-100 ℃, and the sintering pretreatment temperature is 400-700 ℃;
The concentration of the NaOH solution is 10-20wt%, the soaking temperature of the NaOH solution is 50-80 ℃, the heat treatment temperature is 400-700 ℃, the heat treatment time is 0.2-1.5 h, the concentration of the oxalic acid solution is 5-30wt%, the activation temperature is 80-100 ℃, and the sintering pretreatment temperature is 400-700 ℃;
The temperature of the composite electrodeposition in the step (4) is 80-100 ℃, the current density is 1-5A/dm 2, the stirring speed is 50-300 rpm, and the composite electrodeposition time is 4-20 h; the manganese nitrate composite plating solution contains 20-100 g/L manganese nitrate, 2-30 g/L nitric acid, 10-40 g/L sodium tungstate, 10-30 g/L Ag-doped carbon fiber-beta-PbO 2 composite particles and 4-30 g/L Sn-Ru-TaOx coated hollow glass microspheres.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210928867.8A CN115287737B (en) | 2022-08-03 | 2022-08-03 | Titanium-based gradient composite manganese dioxide anode plate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210928867.8A CN115287737B (en) | 2022-08-03 | 2022-08-03 | Titanium-based gradient composite manganese dioxide anode plate and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115287737A CN115287737A (en) | 2022-11-04 |
| CN115287737B true CN115287737B (en) | 2024-07-02 |
Family
ID=83827176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210928867.8A Active CN115287737B (en) | 2022-08-03 | 2022-08-03 | Titanium-based gradient composite manganese dioxide anode plate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115287737B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113862759B (en) * | 2021-10-29 | 2024-05-10 | 昆明理工大学 | Titanium-based gradient lead dioxide composite electrode material for copper electrodeposition and preparation method thereof |
| CN116666648B (en) * | 2023-06-26 | 2024-10-01 | 昆明理工恒达科技股份有限公司 | Aluminum-based composite polar plate for high-capacity long-service-life lead-carbon energy storage battery and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011190466A (en) * | 2009-03-11 | 2011-09-29 | Fujifilm Corp | Aluminum alloy substrate, and substrate for solar cell |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4554063B2 (en) * | 2000-12-19 | 2010-09-29 | 東邦チタニウム株式会社 | Method for forming titanium oxide film and titanium electrolytic capacitor |
| TW533440B (en) * | 2000-12-19 | 2003-05-21 | Toho Titanium Co Ltd | Method for forming titanium oxide film and titanium electrolytic capacitor |
| US20040121290A1 (en) * | 2002-09-16 | 2004-06-24 | Lynntech, Inc. | Biocompatible implants |
| EP1618575B1 (en) * | 2003-04-28 | 2019-10-23 | Showa Denko K.K. | Valve acting metal sintered body, production method therefor and solid electrolytic capacitor |
| US7760487B2 (en) * | 2007-10-22 | 2010-07-20 | Avx Corporation | Doped ceramic powder for use in forming capacitor anodes |
| JP2010263037A (en) * | 2009-05-01 | 2010-11-18 | Fujifilm Corp | Metal composite substrate and method of producing the same |
| US8512422B2 (en) * | 2010-06-23 | 2013-08-20 | Avx Corporation | Solid electrolytic capacitor containing an improved manganese oxide electrolyte |
| JP5744313B2 (en) * | 2011-04-05 | 2015-07-08 | エルジー・ケム・リミテッド | Negative electrode active material for lithium secondary battery and method for producing the same |
| CN107190275A (en) * | 2011-04-05 | 2017-09-22 | 辉光能源公司 | Electrochemical hydrogen-catalyst power system based on water |
| EA201691042A1 (en) * | 2013-11-20 | 2016-12-30 | Бриллиант Лайт Пауэр, Инк. | SYSTEMS AND METHODS OF ENERGY GENERATION |
| SG11201609924RA (en) * | 2014-05-29 | 2016-12-29 | Brilliant Light Power Inc | Electrical power generation systems and methods regarding same |
| US20160028081A1 (en) * | 2014-07-22 | 2016-01-28 | Xerion Advanced Battery Corporation | Lithiated transition metal oxides |
| CN104562094B (en) * | 2015-01-20 | 2016-11-16 | 昆明理工恒达科技股份有限公司 | A kind of preparation method of non-ferrous metal electrodeposition graded composite anode |
| US20170207464A1 (en) * | 2016-01-15 | 2017-07-20 | Elod Lajos Gyenge | Oxygen electrode and a method of manufacturing the same |
| CN107723747B (en) * | 2017-10-17 | 2019-04-19 | 昆明理工大学 | Zinc electrolysis ti-supported lead dioxide electric/manganese dioxide gradient electrode and preparation method thereof |
| CN108677221B (en) * | 2018-06-13 | 2020-06-16 | 昆明理工大学 | Titanium-based β -MnO2Composite coating anode and preparation method thereof |
| CN109023436B (en) * | 2018-07-23 | 2020-08-25 | 昆明理工大学 | Titanium-based β -MnO2-RuO2Composite coating anode plate and preparation method and application thereof |
| CN108823603B (en) * | 2018-09-03 | 2023-08-15 | 昆明理工恒达科技股份有限公司 | Fence type composite anode plate for copper electrodeposition and preparation method thereof |
| CA3124016A1 (en) * | 2019-01-18 | 2020-07-23 | Brilliant Light Power, Inc. | Magnetohydrodynamic hydrogen electrical power generator |
| US20220042189A1 (en) * | 2020-08-05 | 2022-02-10 | Battelle Energy Alliance,Llc | Anodes comprising transition metal and platinum group metal as alloys, and related methods and systems |
| CN113862759B (en) * | 2021-10-29 | 2024-05-10 | 昆明理工大学 | Titanium-based gradient lead dioxide composite electrode material for copper electrodeposition and preparation method thereof |
-
2022
- 2022-08-03 CN CN202210928867.8A patent/CN115287737B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011190466A (en) * | 2009-03-11 | 2011-09-29 | Fujifilm Corp | Aluminum alloy substrate, and substrate for solar cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115287737A (en) | 2022-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103205780B (en) | Grate type titanium-based PbO2 electrode for nonferrous metal electrodeposition and preparation method of grate type titanium-based PbO2 electrode | |
| CN115287737B (en) | Titanium-based gradient composite manganese dioxide anode plate and preparation method thereof | |
| CN100580147C (en) | Method for manufacturing energy-saving inert anode material for non-ferro metals electrodeposition | |
| CN104611731B (en) | Preparation method of fence-type aluminum bar lead alloy anode plate for non-ferrous metal electrodeposition | |
| CN101538724B (en) | Method for preparing energy-saving metal-based ceramic inert anode material for nonferrous metal electrowinning | |
| CN101343758B (en) | Method for preparing novel energy conservation inert anode material for zinc electrodeposition | |
| CN101922024B (en) | Light composite electro-catalysis energy-saving anode for non-ferrous metal electro-deposition and preparation method thereof | |
| CN107604388B (en) | Composite anode material and preparation method thereof, anode plate and preparation method thereof | |
| CN111926349B (en) | Composite anode for hydrometallurgy and preparation method and application thereof | |
| CN102888625A (en) | Fence type anode plate for electrodeposition of nonferrous metals | |
| CN104313652B (en) | Preparation method of aluminum-based multiphase inert composite anode material | |
| CN204779871U (en) | Non ferrous metal is fence type anode plate for electrodeposition | |
| CN201220972Y (en) | Energy-saving inert anode sheet for non-ferrous metal electrodeposition | |
| CN102433581B (en) | Method for preparing novel anode material for electro-deposition of nonferrous metals | |
| CN103572331B (en) | The non-ferrous metal electrodeposition manufacture method of palisading type titanio PbO2 anode | |
| CN207276744U (en) | Composite anode materials and positive plate | |
| CN102443822B (en) | Gradient functional inert anode material used for zinc electrodeposition and its preparation method | |
| CN103981541A (en) | Preparation method of non-noble metallic oxide coated electrode | |
| CN108754546B (en) | Porous aluminum bar lead alloy surface coating composite anode for zinc electrodeposition and preparation method thereof | |
| CN114855225B (en) | Aluminum-based lead alloy composite anode plate and preparation method thereof | |
| CN111101153A (en) | Composite anode plate for copper electrodeposition and preparation method thereof | |
| CN113293411B (en) | Gradient composite lead dioxide anode plate and preparation method and application thereof | |
| CN114150348B (en) | WC particle reinforced low-silver lead alloy composite anode plate for nonferrous metal electrodeposition and preparation method | |
| CN115613078A (en) | Fence type titanium-coated copper-based platinum-silver-zirconium-nanometer Ta 2 O 5 Gradient composite anode plate and preparation method thereof | |
| CN115807245A (en) | Energy-saving high-strength fence type composite anode plate for non-ferrous metal electrodeposition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |